U.S. patent number 3,840,391 [Application Number 05/190,706] was granted by the patent office on 1974-10-08 for method for the preparation of thin films by ultra-sonically vaporing solutions into an aerosol.
This patent grant is currently assigned to Commissariat A L'Energie Atomique. Invention is credited to Jean Spitz, Jean-Claude Viguie.
United States Patent |
3,840,391 |
Spitz , et al. |
October 8, 1974 |
METHOD FOR THE PREPARATION OF THIN FILMS BY ULTRA-SONICALLY
VAPORING SOLUTIONS INTO AN AEROSOL
Abstract
Thin films of metal, metallic compounds or other materials are
prepared by ultrasonic atomization of a solution which is intended
to form the material to be deposited, the aerosol which is thus
produced being transported by a carrier gas and deposited on a
heated substrate.
Inventors: |
Spitz; Jean (Gieres,
FR), Viguie; Jean-Claude (Grenoble, FR) |
Assignee: |
Commissariat A L'Energie
Atomique (Paris, FR)
|
Family
ID: |
9063211 |
Appl.
No.: |
05/190,706 |
Filed: |
October 20, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Oct 23, 1970 [FR] |
|
|
70.38371 |
|
Current U.S.
Class: |
427/565;
239/102.2; 427/314; 427/248.1; 427/250 |
Current CPC
Class: |
G03F
1/68 (20130101); G03F 1/54 (20130101); B05B
17/0615 (20130101) |
Current International
Class: |
B05B
17/04 (20060101); B05B 17/06 (20060101); G03F
1/08 (20060101); B44d 001/08 () |
Field of
Search: |
;117/DIG.8,105,105.1,107,17.2R,118,124R,16R,5.5,14R,54,127
;118/300 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Whitby; Edward G.
Attorney, Agent or Firm: Cameron, Kerkam, Sutton, Stowell
& Stowell
Claims
What we claim is:
1. Process for the evaporation of a thin layer on a metallic base
by projecting on a heated substrate an aerosol of a solution
including the materials to be deposited on contact with the heated
substrate, the steps of forming an aerosol by atomizing the
solution by ultra-sonic waves, directing this aerosol toward the
heated substrate by a carrier gas, controlling the quantity of
aerosol produced by the power of the ultra-sonic waves, regulating
the size of the droplets of the aerosol by the frequency of the
ultra-sonic waves and regulating the quantity of aerosol projected
on the heated substrate by the amount of the carrier gas.
2. A method according to claim 1, wherein an additional flow of
carrier gas is injected between the atomization zone and the
deposition zone.
3. A method according to claim 1, wherein the solution is atomized
by ultrasonic waves at a frequency of the order of 1 megacycle.
Description
This invention relates to a method and a device for preparing thin
films of metals or metallic compounds by depositing on a heated
substrate a mist of solution which forms the material to be
deposited, the mist being transported towards the substrate by a
carrier gas. The invention also relates to the improved thin films
which are obtained by application of the method.
Up to the present time, the practice which has usually been adopted
for the preparation of thin films in accordance with the method
defined above has consisted in atomizing the solution of material
to be deposited by compressed-air spraying. However, this
particular technique is attended by a number of disadvantages. In
the first place, the mists or aerosols which are obtained are not
homogeneous or, in other words, the droplets have a broad
size-distribution spectrum. In point of fact, as will be explained
hereinafter, an unduly high proportion of droplets which are either
too far below or too far above the optimum size results in
unsatisfactory films, in the former case because the film does not
adhere to the substrate and in the latter case because the
thickness of the film is not uniform. In the second place, the only
available parameter for modifying the characteristics of the mist
(size of droplets and flow rate of aerosol) in a given apparatus is
the flow rate of the carrier gas which is in turn dependent on the
pressure of admission of said gas. In point of fact, it would prove
desirable in many instances to modify the value of only one of the
foregoing characteristics without thereby modifying the value of
the other since any general control is at best a mere
compromise.
The chief aim of the invention is to provide a method of
preparation of thin films which largely overcomes the disadvantages
attached to methods of the prior art. To this end, the invention
proposes a method whereby the solution employed for forming the
material to be deposited is atomized by ultrasonic waves.
The large number of advantages which accrue from the replacement of
compressed-air atomization by ultrasonic atomization are closely
linked with the particular application which is contemplated: the
size distribution is limited to a very narrow range in the vicinity
of the maximum value, thereby ensuring higher quality of films. The
corollary to this is that the efficiency is greatly enhanced since
practically the entire quantity of formed droplets is entrained by
the carrier gas whereas in the case of the compressed-air spraying
process, droplets representing a very high proportion (often higher
than 80 percent) are too large to permit entrainment by the carrier
gas. These droplets are deposited on the walls of the atomization
chamber. There is a complete separation of functions between the
carrier gas and the ultrasonic generator inasmuch as the gas serves
only to entrain the aerosol which has already formed. It is thus
possible to modify the supply of aerosols by acting on the flow
rate of the carrier gas and to modify two parameters by acting on
two separate and distinct properties of the ultrasonic generator
which have practically independent functions: the mean size of the
droplets is dependent on the frequency, the emission from the
solution is dependent on the ultrasonic power.
In short, an improvement is achieved both in the quality of the
aerosol (by narrowing the size distribution spectrum of the
droplets) and in the flexibility of use of the system. In
consequence, it is always much easier to operate under optimum
conditions. Moreover, the aerosol exhibits properties which are
extremely close to those of a homogeneous gas, thereby facilitating
transport of the aerosol from the formation zone to the deposition
zone.
The method according to the invention is primarily although not
exclusively applicable to the preparation of thin oxide films which
may be employed as photo-masks in micro-electronics, of thin films
of sulphides and garnets as well as thin coatings of metals or
metallic compounds (for example aluminum on a metallic or plastic
substrate; nickel, chromium, cobalt, platinum, palladium, osmium,
iridium on a suitable substrate for forming catalysts; and so
forth).
The invention will now be described by way of example with
reference to the accompanying drawings, wherein:
FIG. 1 shows diagrammatically an installation for the formation of
thin films on a flat substrate of large size, the aerosol generator
and the chamber in which the deposition is carried out being shown
in cross-section along a vertical plane;
FIG. 2 is a curve representing the mean diameter of the droplets as
a function of the frequency of the ultrasonic generator;
FIG. 3 is a curve representing the coefficient of transmission of a
thin film of iron oxide Fe.sub.2 O.sub.3 as obtained by means of
the device of FIG. 1 and having a thickness of 2000 A, as a
function of the wavelength of light;
FIG. 4 shows an alternative form of construction of the device of
FIG. 1 for forming deposits on substrates having small dimensions,
the aerosol generator being shown only by way of schematic
illustration;
FIG. 5 shows another alternative form of construction which is
intended for continuous or semicontinuous operation;
FIG. 6 shows the curve of variation of temperature along the
furnace of FIG. 5 when the loaded gas is admitted (full-line curve)
and when no gas is present (dashed-line curve).
The device which is illustrated in FIG. 1 can be considered as
being made up of an aerosol generator A, a deposition chamber B and
ancillary elements. Said device is intended to form thin films on
glass plates 10 having substantial dimensions (e.g. square plates
50 .times. 50 mm in size).
The aerosol generator A has a general structure which is known per
se and a complete description of said generator can be found in the
article by J. Spitz and J. Uny entitled "Ultrasonic spraying
applied to atomic absorption spectrometry" and published in the
July, 1968 issue of "Applied Optics," pages 1345 to 1349. This
generator comprises an ultrasonic-wave emitter 12 which is placed
on the underside of an annular tank 14 containing an
ultransonic-wave transmitting liquid. A diaphram 16 closes-off a
spray atomization chamber 18. The chamber 18 is constituted by a
cylindrical tube provided at the top with a conical end portion in
which is inserted a head 20. The head carries a duct 22 through
which the aerosols are discharged. The carrier gas which may
consist, for example, of argon or of another inert or oxidizing gas
in the case of oxide deposition is introduced into the chamber 18
through a vertical tube 24 which is placed in the axis of the tube
and passes through a stopper 26 which is inserted in the head 20.
The chamber 18 is fitted with a device (not shown) for the
automatic supply of solution of material to be deposited.
The piezoelectric generator 12 is advantageously of a type which
provides for power variation between 0 and 100 W, for example. A
frequency of the order of 1 megacycle is usually suitable and makes
it possible to obtain a mean particle size of a few microns. Tests
carried out with a generator of the type illustrated in FIG. 1 and
using various frequencies have shown that the droplets obtained had
a mean diameter which was a decreasing function of the frequency,
as shown in FIG. 2. Moreover, these tests have demonstrated the
fact that the size spectrum always remains much narrower than in
the case of the compressed-air spraying technique. By way of
example, it can be mentioned that, in the case of a frequency of 3
megacycles, 50 percent of the atomized volume had a diameter
between 2 and 3 microns whilst 27 percent had a volume between 1.5
and 2 microns. The volume atomized in the form of droplets having a
size less than 1.5 microns was practically negligible.
The advantage of this homogeneity is quite clear if the mechanism
of the deposition process is borne in mind: when a droplet of a
solution containing a metallic salt moves towards a heated
substrate, said droplet vaporizes and liberates the metallic salt
in fused form and then in the form of vapor. The salt which is
highly reactive usually reacts on the actual surface of the
substrate since energy transfers are more readily carried out at
this point, whereupon a thin film is formed. However, if the
droplet is too small, vaporization takes place too soon (that is to
say at a distance from the substrate), the reaction is in
homogeneous phase and the solid substance which results does not
adhere strongly on the substrate. Conversely, if vaporization takes
place too late, the droplet is flattened against the substrate and
the accumulations of the deposit at the point of impacts are
detrimental to the quality of the film.
It is therefore apparent that all the drops of an aerosol must
essentially have the same behavior at a given distance from the
substrate and that the dimensions of said drops should accordingly
be maintained within a very narrow range.
In some cases, it is an advantage to be able to adjust the
concentration of aerosols in the carrier gas without acting on the
flow rate of gas above the solution which is subjected to the
action of the ultrasonic generator since said flow rate must remain
of low value in order to prevent "impaction" of the mist which is
formed. In order to ensure compatibility of these two requirements,
it is only necessary to provide the duct 22 with a branch pipe 38
for the supply of argon, said pipe being fitted with a
flow-regulating valve 40. It should be noted in this connection
that the very uniform aerosol which is delivered by the device A
can be transported by a gas flow at a very low rate and at a
pressure in the vicinity of atmospheric, with the result that the
air stream which is directed towards the substrate has a low rate
of flow and accordingly cools this latter to a lesser extent.
The deposition chamber which is illustrated in FIG. 1 comprises a
bell-housing 42 which rests on a base 44. Said base is fitted with
a plate 46 which carries the substrate 10 and is heated by a
resistor 48. A motor which is not illustrated serves to displace
the substrate over the plate at a low and uniform speed in order to
increase the homogeneity of the film. A bell-housing having a
diameter of 200 mm and a height of 150 mm has made it possible to
treat glass plates measurng 50 .times. 50 mm. The bell-housing is
provided at the top with a necked portion 50 which is closed by a
head 52 and this latter delimits a chamber 54 into which opens the
duct 22. The aerosol is distributed above the plate 10 by means of
a hollow rod 56 fitted with a nozzle 58 for distribution towards a
number of zones of the substrate. The aerosol penetrates into the
rod through openings 59. The rod 56 is driven in rotation in order
to deliver the aerosol successively over a number of different
portions of the substrate 10 and in order to prevent abrupt and
general cooling of this latter. In the particular example of
preparation of Fe.sub.2 O.sub.3 films which can be considered as
representative, the temperature of the substrate which was
initially of the order of 490.degree.C cannot be caused to vary to
a greater extent than a few tens of degrees, this result being
achieved by virtue of the rotary motion of the rod.
The low flow rate of carrier gas which is permitted by the
uniformity of the aerosol makes it possible to operate at higher
temperatures than in devices of the prior art which make use of the
compressed-air atomization technique.
There will now be described by way of example the formation of thin
films of ferric oxide which can be employed as photo-masks. Up to
the present time, the majority of photo-masks which were employed
in the fabrication of integrated electronic circuits were made of
chromium. However, chromium masks are opaque to visible light, with
the result that relative positioning of the different masks is a
difficult operation. On the contrary, the ferric oxide films which
are obtained by application of the method according to the
invention are transparent in the visible region of the spectrum so
that it is possible to position them accurately and to reduce
manufacturing rejects.
The tests which have been carried out with a generator having an
output freqency of 1 Mc/s acting on an aqueous solution of ferric
chloride FeCl.sub.3 having a concentration of 0.4 mole/liter in an
argon stream flowing at a rate of 6 1/min and at a pressure which
is very close to atmospheric have made it possible to form thin
films of this type on a substrate which was maintained at a minimum
temperature of 450.degree.C. The crystallites obtained are very
small since their dimensions are of the order of 2,000 A and are
extremely uniform. The photo-masks which are thus produced achieve
perfect compliance with the conditions laid down, that is to say
good transmission of light in the visible region of the spectrum
and low transmission in the ultraviolet region below 4,000 A, as
shown in FIG. 3. Since the crystallites are extremely small,
chemical etching can be highly accurate. Finally, hardness and
resistance to abrasion are very high. It should be noted in this
connection that the size of the crystallites obtained by means of
the compressed-air spraying process remains of the order of one
micron. The technical advance which has been made is therefore of
considerable significance. Instead of ferric chloride in water, use
can be made of a ferric organic salt in solution in a volatile
solvent which can be organic in order to be destroyed at the time
of formation, for example by combustion in the oxidizing carrier
gas.
The device which is illustrated in FIG. 4 constitutes an
alternative embodiment of the invention which is intended for the
formation of garnets in a thin film on substrates having smaller
dimensions than in the previous example, the substrates being made
up of quartz plates measuring 15 .times. 15 mm at a temperature
which is higher than in the previous example and which can attain
800.degree.C.
The aerosol generator A' is connected by a short length of piping
to the chamber B'. Said chamber is constituted by a tube which is
provided at the lower end with an additional argon inlet 38' and in
which is placed a nozzle 58' for directing the aerosol onto the
substrate 10'. The top portion of the tube 42' is placed within a
sleeve 62, said sleeve being in turn placed within an electric
resistance-type tubular furnace 64. Growth of the film is indicated
by a recorder 70 which is connected to a photoresistive cell 66,
said cell being placed in an end-piece 68 which closes the sleeve
and being illuminated by a light source 67. The temperature of the
substrate 10' is measured by a thermocouple (not shown) which
controls a regulating device for maintaining the substrate at a
suitable temperature.
In this embodiment, vaporization is carried out slowly as the
carrier gas loaded with droplets progresses within the nozzle
58'.
The device which is illustrated in FIG. 5 differs from the
preceding in that it is designed for either continuous or
semi-continuous operation. The aerosol generator A" is very similar
to the generator shown in FIG. 1 but the vertical tube 24" extends
into a bubbling flask 72 which also contains the addition solution.
The gas is saturated with solvent in said flask and passes out of
this latter through apertures 74, then entrains the mist which was
formed in the chamber 18" towards a discharge pipe 22".
The deposition chamber B" has a generally flat shape and is
provided with two slits in its opposite faces. An endless strip 76
which is driven and guided by two pulleys 78 as shown very
diagrammatically in FIG. 5 passes into the chamber and out of this
latter through said slits. Recesses 78, one of which is shown on a
large scale on the top left-hand side of FIG. 5, are formed in the
strip 76. Each recess is intended to receive a substrate 10" on
which a thin film is to be deposited.
Two sets of resistors constituting a furnace 64" are placed within
the deposition chamber on each side of the path of the endless
strip 76. The temperature distribution within said furnace
advantageously comprises two lateral portions which permit rapid
variation and are as small in length as possible and a central
portion having a substantially constant temperature. However, it is
usually sufficient in practice to have a curve of variation of the
type illustrated in FIG. 6 with a minimum value at the center which
is not very pronounced and results from the injection of gas.
The nozzle 58" could be flat and perpendicular to the direction of
displacement of the endless strip 76 but it is usually an advantage
to ensure that said nozzle has a generally cylindrical shape and is
driven in a reciprocating movement of translation at right angles
to the direction of displacement of the strip. In FIG. 5, the
nozzle is carried by the plunger 80 and this latter is slidably
mounted within a cylinder 82 which is carried by an extension of
the chamber B". The plunger is coupled to a motor (not shown) and
endowed by this latter with the necessary reciprocating motion.
The invention is clearly not limited solely to the embodiments whch
have been illustrated and described by way of example but extends
to all alternative forms, and in particular the application to
deposits which are not limited solely to metallic constituents.
* * * * *